ABS (Acrylonitrile Butadiene Styrene) composite material with flame retardant effect and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and particularly discloses an ABS (acrylonitrile-butadiene-styrene) composite material with a flame-retardant effect and a preparation method of the ABS composite material. The ABS composite material with the flame retardant effect comprises the following components in parts by weight: 50-100 parts of ABS resin; 10 to 30 parts of PA6 resin; 15-30 parts of a composite flame retardant; 1-10 parts of a compatilizer; 1-3 parts of a lubricant; and 1-3 parts of an antioxidant. According to the ABS composite material disclosed by the invention, the composite flame retardant is added into the ABS composite material, so that the ABS composite material has excellent flame retardant property.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to an ABS composite material with flame retardant effect and a preparation method thereof. Background Art

[0002] A terpolymer obtained by polymerizing acrylonitrile (A), butadiene (B) and styrene (S); it is a thermoplastic polymer material with high strength, good toughness and easy processing and molding; at the same time, due to its advantages such as easy availability of raw materials, good comprehensive performance and low price, it has been widely used in the fields of automobiles, aircraft, ships, and electricity.

[0003] For example, Chinese invention patent CN202011370654.5 discloses an ABS composite material, its preparation method and application, wherein the composite material comprises the following components in percentage by mass: PA6 resin: 15-30 parts; ABS resin I: 25-45 parts; ABS resin II: 10-40 parts; toughener: 5-10 parts; compatibilizer: 3-10 parts; styrene monomer: 0.2-1 parts; processing aid: 0.5-1.5 parts. The ABS composite material has excellent low stress whitening and chemical resistance. However, studies have shown that the flame retardant properties of the ABS composite material need to be further improved. Summary of the invention

[0004] In order to overcome at least one of the technical problems existing in the prior art, the present invention provides an ABS composite material with flame retardant effect and a preparation method thereof.

[0005] The above technical problems to be solved by the present invention are solved by the following technical solutions:

[0006] The present invention firstly provides an ABS composite material with flame retardant effect, which comprises the following components in parts by weight: 50-100 parts of ABS resin; 10-30 parts of PA6 resin; 15-30 parts of composite flame retardant; 1-10 parts of compatibilizer; 1-3 parts of lubricant; and 1-3 parts of antioxidant.

[0007] The present invention provides a flame-retardant ABS composite material of a completely new composition; the present invention adds a composite flame retardant into the ABS composite material, so that the ABS composite material has excellent flame retardant performance.

[0008] Preferably, the flame-retardant ABS composite material comprises the following components in parts by weight: 70-80 parts of ABS resin; 20-30 parts of PA6 resin; 20-30 parts of composite flame retardant; 1-5 parts of compatibilizer; 1-2 parts of lubricant; and 1-2 parts of antioxidant.

[0009] Most preferably, the flame retardant ABS composite material comprises the following components in parts by weight: 80 parts of ABS resin; 20 parts of PA6 resin; 20 parts of composite flame retardant; 5 parts of compatibilizer; 1 part of lubricant; and 1 part of antioxidant.

[0010] Preferably, the composite flame retardant comprises resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and mica powder.

[0011] Preferably, the weight ratio of resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and mica powder in the composite flame retardant is 1-3:1-5:5-10.

[0012] Most preferably, the weight ratio of resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and mica powder in the composite flame retardant is 2:3:8.

[0013] Preferably, the mica powder is modified mica powder.

[0014] Preferably, the modified mica powder is prepared by the following method:

[0015] (1) adding mica powder into water, and then adding a modifier and mixing evenly to obtain a modified mixed solution;

[0016] (2) The modified mixed solution is placed in a ball mill for ball milling for 2 to 5 hours. After the ball milling is completed, the ball milled mixture is dried to obtain the modified mica powder.

[0017] The inventors found in further research that the impact resistance of the ABS composite material needs to be further improved. A large number of studies have shown that adding the modified mica powder prepared by the above method to the composite flame retardant can greatly improve the impact resistance of the ABS composite material.

[0018] Preferably, the modifier in step (1) consists of 3-ureidopropyltrimethoxysilane and sodium dioctyl dibutyrate sulfonate.

[0019] The inventors found in further research that the composition of the modifier is very critical in the preparation process of the modified mica powder. The study shows that the modifier composed of 3-ureidopropyl trimethoxysilane and sodium dioctyl dibutyrate sulfonate must be added at the same time to significantly improve the impact resistance of the ABS composite material; however, adding a single 3-ureidopropyl trimethoxysilane or sodium dioctyl dibutyrate sulfonate cannot significantly improve the impact resistance of the ABS composite material. In the preparation process of the modified mica powder, adding a modifier composed of 3-ureidopropyl trimethoxysilane and sodium dioctyl dibutyrate sulfonate at the same time can synergistically improve the impact resistance of the ABS composite material.

[0020] Preferably, the weight ratio of 3-ureidopropyltrimethoxysilane to sodium dioctyl dibutyrate sulfonate is 1 to 3:1.

[0021] Most preferably, the weight ratio of 3-ureidopropyltrimethoxysilane to sodium dioctyl dibutyrate sulfonate is 2:1.

[0022] Preferably, in step (1), the weight ratio of mica powder to modifier and water is 5-10:1-3:20-50.

[0023] Most preferably, in step (1), the weight ratio of mica powder to modifier and water is 8:2:35.

[0024] Preferably, the lubricant is selected from calcium stearate.

[0025] Preferably, the antioxidant is selected from antioxidant 1010.

[0026] The present invention also provides a method for preparing the above-mentioned ABS composite material with flame retardant effect, which comprises the following steps:

[0027] The ABS resin, PA6 resin, composite flame retardant, compatibilizer, lubricant and antioxidant are uniformly mixed and then melt-extruded through a twin-screw extruder to obtain the ABS composite material with flame retardant effect.

[0028] Beneficial effects: The present invention provides a flame-retardant ABS composite material with a new composition; the present invention adds a composite flame retardant to the ABS composite material, so that the ABS composite material has excellent flame retardant properties. DETAILED DESCRIPTION

[0029] The present invention is further explained below in conjunction with specific examples, but the examples do not limit the present invention in any form.

[0030] The ABS resin described in the following embodiments is ABS resin with the brand PA-797 produced by Chi Mei in Taiwan, China; the PA6 resin is PA6 resin with the brand B3K produced by BASF in Germany; the compatibilizer is SEBS elastomer with the brand FG1901GT produced by Kraton in the United States; the remaining raw materials whose sources are not specified are conventional raw materials that can be purchased by technicians in this field through conventional purchasing channels.

[0031] Example 1 Preparation of ABS composite material with flame retardant effect

[0032] The raw materials are composed by weight: 80 parts of ABS resin; 20 parts of PA6 resin; 20 parts of composite flame retardant; 5 parts of compatibilizer; 1 part of lubricant (calcium stearate); and 1 part of antioxidant (antioxidant 1010).

[0033] The composite flame retardant consists of resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and mica powder in a weight ratio of 2:3:8.

[0034] Example 2 Preparation of ABS composite material with flame retardant effect

[0035] The raw materials are composed by weight: 80 parts of ABS resin; 20 parts of PA6 resin; 20 parts of composite flame retardant; 5 parts of compatibilizer; 1 part of lubricant (calcium stearate); and 1 part of antioxidant (antioxidant 1010).

[0036] The composite flame retardant is composed of resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and modified mica powder in a weight ratio of 2:3:8;

[0037] The modified mica powder is prepared by the following method:

[0038] (1) adding mica powder to water, and then adding a modifier and mixing them evenly to obtain a modified mixed solution; wherein the weight ratio of the mica powder to the modifier and water is 8:2:35; and the modifier is composed of 3-ureidopropyltrimethoxysilane and sodium dioctyl dibutyrate sulfonate in a weight ratio of 2:1;

[0039] (2) The modified mixed solution is placed in a ball mill for ball milling for 4 hours. After the ball milling is completed, the ball milled mixture is dried to obtain the modified mica powder.

[0040] Example 3 Preparation of ABS composite material with flame retardant effect

[0041] The raw materials are composed by weight: 50 parts of ABS resin; 10 parts of PA6 resin; 15 parts of composite flame retardant; 1 part of compatibilizer; 1 part of lubricant (calcium stearate); and 1 part of antioxidant (antioxidant 1010).

[0042] The composite flame retardant is composed of resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and modified mica powder in a weight ratio of 1:5:5;

[0043] The modified mica powder is prepared by the following method:

[0044] (1) adding mica powder to water, and then adding a modifier and mixing them evenly to obtain a modified mixed solution; wherein the weight ratio of the mica powder to the modifier and water is 10:3:50; the modifier is composed of 3-ureidopropyltrimethoxysilane and sodium dioctyl dibutyrate sulfonate in a weight ratio of 1:1;

[0045] (2) The modified mixed solution is placed in a ball mill for ball milling for 3 hours. After the ball milling is completed, the ball milled mixture is dried to obtain the modified mica powder.

[0046] Example 4 Preparation of ABS composite material with flame retardant effect

[0047] The raw materials are composed by weight: 100 parts of ABS resin; 30 parts of PA6 resin; 30 parts of composite flame retardant; 10 parts of compatibilizer; 3 parts of lubricant (calcium stearate); and 3 parts of antioxidant (antioxidant 1010).

[0048] The composite flame retardant is composed of resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and modified mica powder in a weight ratio of 3:1:10;

[0049] The modified mica powder is prepared by the following method:

[0050] (1) adding mica powder to water, and then adding a modifier and mixing them evenly to obtain a modified mixed solution; wherein the weight ratio of the mica powder to the modifier and water is 5:1:20; and the modifier is composed of 3-ureidopropyltrimethoxysilane and sodium dioctyl dibutyrate sulfonate in a weight ratio of 1:1;

[0051] (2) The modified mixed solution is placed in a ball mill for ball milling for 5 hours. After the ball milling is completed, the ball milled mixture is dried to obtain the modified mica powder.

[0052] Comparative Example 1 Preparation of ABS composite material with flame retardant effect

[0053] The raw materials are composed by weight: 80 parts of ABS resin; 20 parts of PA6 resin; 20 parts of composite flame retardant; 5 parts of compatibilizer; 1 part of lubricant (calcium stearate); and 1 part of antioxidant (antioxidant 1010).

[0054] The composite flame retardant is composed of resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and modified mica powder in a weight ratio of 2:3:8;

[0055] The modified mica powder is prepared by the following method:

[0056] (1) adding mica powder to water, and then adding a modifier and mixing evenly to obtain a modified mixed solution; wherein the weight ratio of mica powder to the modifier and water is 8:2:35; and the modifier is 3-ureidopropyltrimethoxysilane;

[0057] (2) The modified mixed solution is placed in a ball mill for ball milling for 4 hours. After the ball milling is completed, the ball milled mixture is dried to obtain the modified mica powder.

[0058] Comparative Example 2 Preparation of ABS composite material with flame retardant effect

[0059] The raw materials are composed by weight: 80 parts of ABS resin; 20 parts of PA6 resin; 20 parts of composite flame retardant; 5 parts of compatibilizer; 1 part of lubricant (calcium stearate); and 1 part of antioxidant (antioxidant 1010).

[0060] The composite flame retardant is composed of resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and modified mica powder in a weight ratio of 2:3:8;

[0061] The modified mica powder is prepared by the following method:

[0062] (1) adding mica powder to water, and then adding a modifier and mixing evenly to obtain a modified mixed solution; wherein the weight ratio of mica powder to the modifier and water is 8:2:35; and the modifier is sodium dioctyl dibutyrate sulfonate;

[0063] (2) The modified mixed solution is placed in a ball mill for ball milling for 4 hours. After the ball milling is completed, the ball milled mixture is dried to obtain the modified mica powder.

[0064] The flame retardant grade of the flame retardant ABS composite materials prepared according to Examples 1 to 2 and Comparative Examples 1 to 2 was tested according to the method in the UL-94 standard; the simply supported beam notched impact strength was tested according to the method in the ISO 179-1:2010 standard; the test results are shown in Table 1.

[0065] Table 1. Test results of flame retardant ABS composite materials

[0066]

[0067] It can be seen from the experimental results in Table 1 that the flame retardant ABS composite materials prepared in Examples 1 and 2 have a flame retardant grade of V-0; this shows that the present invention adds a composite flame retardant to the ABS composite material, so that the ABS composite material has excellent flame retardant properties.

[0068] It can be seen from the experimental results in Table 1 that the notched impact strength of the flame-retardant ABS composite material prepared in Example 2 is much higher than that of the flame-retardant ABS composite material prepared in Example 1; this indicates that adding the modified mica powder prepared by the above method to the composite flame retardant can greatly improve the impact resistance of the ABS composite material.

[0069] It can be seen from the experimental results in Table 1 that the notched impact strength of the flame-retardant ABS composites prepared in Comparative Examples 1 and 2 is not much improved compared with the flame-retardant ABS composites prepared in Example 1, and is much smaller than the flame-retardant ABS composites prepared in Example 2; this shows that in the preparation process of modified mica powder, the composition of the modifier is very critical. The above results show that the modifier composed of 3-ureidopropyl trimethoxysilane and sodium dioctyl dibutyrate sulfonate must be added at the same time to significantly improve the impact resistance of the ABS composite; however, adding a single 3-ureidopropyl trimethoxysilane or sodium dioctyl dibutyrate sulfonate cannot significantly improve the impact resistance of the ABS composite. In the preparation process of modified mica powder, adding a modifier composed of 3-ureidopropyl trimethoxysilane and sodium dioctyl dibutyrate sulfonate at the same time can synergistically improve the impact resistance of the ABS composite.

Claims

1. An ABS composite material with flame retardant effect, characterized in that: The invention comprises the following components in parts by weight: 50 to 100 parts of ABS resin; 10 to 30 parts of PA6 resin; 15 to 30 parts of composite flame retardant; 1 to 10 parts of compatibilizer; 1 to 3 parts of lubricant; and 1 to 3 parts of antioxidant.

2. The flame retardant ABS composite material according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 70-80 parts of ABS resin; 20-30 parts of PA6 resin; 20-30 parts of composite flame retardant; 1-5 parts of compatibilizer; 1-2 parts of lubricant; and 1-2 parts of antioxidant.

3. The flame retardant ABS composite material according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 80 parts of ABS resin; 20 parts of PA6 resin; 20 parts of composite flame retardant; 5 parts of compatibilizer; 1 part of lubricant; and 1 part of antioxidant.

4. The flame retardant ABS composite material according to claim 1, characterized in that: The composite flame retardant comprises resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and mica powder.

5. The flame retardant ABS composite material according to claim 1, characterized in that: The weight ratio of resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and mica powder in the composite flame retardant is 1-3:1-5:5-10.

6. The flame retardant ABS composite material according to claim 5, characterized in that: The weight ratio of resorcinol bis(diphenyl phosphate), diethyl aluminum hypophosphite and mica powder in the composite flame retardant is 2:3:

8.

7. The flame retardant ABS composite material according to claim 5, characterized in that: The mica powder is modified mica powder.

8. The flame retardant ABS composite material according to claim 7, characterized in that: The modified mica powder is prepared by the following method: (1) adding mica powder into water, and then adding a modifier and mixing evenly to obtain a modified mixed solution; (2) The modified mixed solution is placed in a ball mill for ball milling for 2 to 5 hours. After the ball milling is completed, the ball milled mixture is dried to obtain the modified mica powder.

9. The flame retardant ABS composite material according to claim 8, characterized in that: The modifier in step (1) consists of 3-ureidopropyltrimethoxysilane and sodium dioctyl dibutyrate sulfonate.

10. The method for preparing the flame retardant ABS composite material according to any one of claims 1 to 9, characterized in that: The following steps are included: The ABS resin, PA6 resin, composite flame retardant, compatibilizer, lubricant and antioxidant are uniformly mixed and then melt-extruded through a twin-screw extruder to obtain the ABS composite material with flame retardant effect.

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